JP2007314833A - Hydrogen-producing apparatus and hydrogen-producing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a hydrogen-producing apparatus, which continuously electrolyzes high-temperature water vapor by retaining electrical insulation characteristics and maintaining airtightness while keeping mechanical strength. <P>SOLUTION: The hydrogen-producing apparatus comprises: a cylindrical electrochemical cell 1 which is made from ceramics, and includes a hydrogen pole 9 that forms a cylindrical inner side with one end closed, a cylindrical oxygen pole 11 installed outside the hydrogen pole 9, and an electrolyte layer 10 that has electron-insulating properties and electroconductivity for oxygen ions, and is provided between the hydrogen pole 9 and the oxygen pole 11; a water vapor introduction pipe 6 which is arranged in the cylindrical electrochemical cell 1 and introduces water vapor into the cell; a unit container 2 for accommodating the cylindrical electrochemical cell 1; a cell-supporting plate 15 which is fixed in the unit container 2 and supports the cylindrical electrochemical cell 1; and an insulating and sealing means 7 which is installed between the cell-supporting plate 15 and the cylindrical electrochemical cell 1, electrically insulate them to each other, and seal the gap between them. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a hydrogen production apparatus and method for producing hydrogen by high-temperature steam electrolysis.

  As one vision of the future society, the realization of a hydrogen energy society using hydrogen as an energy medium is attracting attention, and several promising hydrogen production methods are considered. Among several hydrogen production methods, the high-temperature steam electrolysis method is a method of electrolyzing water vapor at a high temperature of about 900 ° C., and the same hydrogen production amount can be obtained with about 30% less electric power than water electrolysis at room temperature. It is a hydrogen production method with high energy efficiency. Since the raw material is water, if a heat source that does not generate carbon dioxide is used, hydrogen can be produced without exhausting any carbon dioxide.

  The hydrogen production apparatus using the high-temperature steam electrolysis is configured by arranging a plurality of minimum unit cells. This cell basically has a three-layer structure in which an electrolyte layer is in the middle and an oxygen electrode (anode) and a hydrogen electrode (cathode) are arranged on both sides of the electrolyte layer.

  In the hydrogen electrode, the introduced water vapor is decomposed into oxygen ions and hydrogen by giving electrons. The decomposed oxygen ions pass through the electrolyte layer and emit electrons at the oxygen electrode to generate oxygen. The electrolyte layer, oxygen electrode, and hydrogen electrode are made of ceramics to withstand use at high temperatures.

  Although there are various shapes of the cell, here, as an example, a cylindrical cell in which the three-layer structure is arranged in a concentric cylinder shape will be described. In order to increase the amount of hydrogen produced, a cell unit in which many cylindrical cells are fixed is necessary.

At the place where the cylindrical cell (ceramic) is fixed in the container (metal), there is a connection part between the metal part and the ceramic. This part is required to have a function of isolating hydrogen and oxygen and a function of insulating the oxygen electrode (anode) and the hydrogen electrode (cathode) in addition to the function of connecting the metal part and the ceramic part. As this bonding material, a technique for connecting a metal part and a ceramic part using glass is known (see, for example, Patent Documents 1 and 2).
JP 2003-238201 A JP 2003-173800 A

  In the above-described conventional hydrogen production by high-temperature steam electrolysis, a connecting portion between a metal part (container) and ceramics (cell) is interposed at a location where the cylindrical cell is fixed in the container. Glass is used for this connecting portion so as to withstand high temperature steam electrolysis.

  This connecting portion may be butt-joined depending on manufacturability requirements. In this butt joint, the strength of the joint is weak and may be damaged by vibration or the like. In addition, since straight joining is difficult, there is a problem that the cell is inclined and may come into contact with the water vapor introduction pipe to break the cell.

  Further, in the cylindrical cell, when the structure is such that the hydrogen electrode is disposed on the inner surface and the oxygen electrode is disposed on the outer surface, the water vapor introducing pipe is installed inside the cell. The gap between the outer diameter of the water vapor introducing pipe inserted into the cell and the inner diameter of the cell is small. For this reason, when the water vapor introduction pipe is installed on the support plate by welding, the support plate is deformed, the water vapor introduction pipe is inclined, and the cell and the water vapor introduction pipe interfere with each other and may be damaged.

  Further, if the straightness of the cell is low, the water vapor introducing tube and the cell may come into contact with each other at the tip of the cell, and the cell may be damaged. Furthermore, since the cells are made of ceramics, the roundness of the cells is difficult to achieve, so structural discontinuities tend to occur at the joints of the machined metal support, and stress concentration occurs at the thin-walled portions. There was a problem that there was a risk of breakage.

  Furthermore, when the joint portion is broken, the boundary between hydrogen and oxygen is destroyed, the amount of hydrogen production decreases, and further, there is a problem that hydrogen production cannot be performed.

  The present invention has been made to solve the above-described problems. A hydrogen production apparatus capable of continuously performing a high-temperature steam electrolysis reaction with a boundary between a hydrogen atmosphere and an oxygen atmosphere configured to withstand high temperatures and An object is to provide such a method.

  In order to achieve the above object, in the hydrogen production apparatus of the present invention, a hydrogen electrode which is closed at one end to form a cylindrical inner side, a cylindrical oxygen electrode provided outside the hydrogen electrode, and the hydrogen electrode A cylindrical electrochemical cell made of ceramics, including an electrolyte layer with electronic insulation and oxygen ion conductivity provided between the oxygen electrode and water vapor introduced inside this cylindrical electrochemical cell A water vapor introducing tube, a unit container for housing the cylindrical electrochemical cell, a cell support plate fixed in the unit container and supporting the cylindrical electrochemical cell, the cell supporting plate and the cylindrical electrochemical cell An insulating sealing means provided between the cell and electrically insulating and sealing the produced hydrogen; a water vapor introducing pipe support plate fixed in the unit container and supporting the water vapor introducing pipe; A hydrogen electrode power supply unit provided so that the hydrogen electrode on the inner surface of the cylindrical electrochemical cell serves as a cathode, and an oxygen electrode power supply provided so that the oxygen electrode on the outer surface of the cylindrical electrochemical cell serves as an anode And a portion.

  In order to achieve the above object, in the hydrogen production method of the present invention, one end is closed and a cylindrical inner electrode is formed, a cylindrical oxygen electrode provided outside the hydrogen electrode, and the hydrogen electrode A cylindrical electrochemical cell production step for producing a cylindrical electrochemical cell from ceramics, including an electrolyte layer provided between an electrode and an oxygen electrode and having an electronic insulating property and an oxygen ion conductivity; and fixed in a unit container A water vapor introduction step for introducing water vapor into the inside of the cylindrical electrochemical cell via a water vapor introduction pipe, a hydrogen electrode power feeding step in which the hydrogen electrode on the inner surface of the cylindrical electrochemical cell is used as a cathode, and the cylindrical shape An oxygen electrode feeding step in which the oxygen electrode on the outer surface of the electrochemical cell is used as an anode, a hydrogen generation step in which hydrogen is generated through the cylindrical electrochemical cell, and fixed in the unit container. An insulating sealing step of sealing the electrically insulating and produced hydrogen and cell support plate between said cylindrical electrochemical cell was, is characterized in that it has a.

  According to the hydrogen production apparatus and method of the present invention, a high-strength inorganic material such as alumina is used as an insulating material for a ceramic cylindrical electrochemical cell, and the inorganic material and the support plate in the container are diffused. By connecting by bonding, a boundary that can withstand high temperatures can be formed between a hydrogen atmosphere and an oxygen atmosphere. Thus, an insulating seal having airtightness with excellent electrical insulation and mechanical strength is formed, and a high temperature steam electrolysis reaction can be continuously performed.

  Hereinafter, embodiments of a hydrogen production apparatus and method according to the present invention will be described with reference to the drawings. Here, the same or similar parts are denoted by common reference numerals, and redundant description is omitted.

  FIG. 1 is a schematic longitudinal sectional view showing a configuration of a high-temperature steam electrolysis unit according to a first embodiment of the present invention, and FIG. 2 is a longitudinal sectional view showing a fixing method of the cylindrical electrochemical cell 1 of FIG. FIG. 3 is a longitudinal sectional view showing another fixing method of the cylindrical electrochemical cell 1 of FIG.

  As shown in FIG. 1, a high-temperature steam electrolysis unit that is a hydrogen production apparatus has a plurality of (here, three) cylindrical ceramic cells 1 made of ceramics installed in a unit container 2.

  This cylindrical electrochemical cell 1 has a hydrogen electrode 9 that closes one end and forms a cylindrical inner side. A base tube 8 is provided inside the hydrogen electrode 2 as a base tube as necessary. Moreover, the top part of the cylindrical tube of the hydrogen electrode 9 that closes one end and forms a cylindrical inner side may be disposed upward or downward. Here, the top of the cylindrical tube of the hydrogen electrode 9 is disposed upward.

  A cylindrical oxygen electrode 11 is disposed outside the hydrogen electrode 9. An electrolyte layer 10 having electronic insulation and oxygen ion conductivity is provided between the hydrogen electrode 9 and the oxygen electrode 11.

  Inside the cylindrical electrochemical cell 1, a water vapor introduction pipe 6 for introducing water vapor is provided. The water vapor introduction pipe 6 is fixed to a water vapor introduction pipe support plate 16 constituting the water vapor supply unit 3 in the unit container 2. Water vapor in the water vapor supply unit 3 is introduced into the cylindrical electrochemical cell 1 through the water vapor introduction pipe 6.

  The introduced water vapor is decomposed into oxygen ions and hydrogen by giving electrons at the hydrogen electrode 9. The decomposed oxygen ions pass through the electrolyte layer 10 and release electrons at the oxygen electrode 11 to generate oxygen.

  The generated hydrogen is discharged to the generated hydrogen outlet portion 4 in the unit container 2, and the generated oxygen is discharged to the generated oxygen outlet portion 5 in the unit container 2. The generated hydrogen outlet portion 4 and the generated oxygen outlet portion 5 are separated by a cell support plate 15. An open end of a cylindrical cylindrical electrochemical cell 1 whose one end is closed is fixed to the cell support plate 15.

  Further, a hydrogen electrode power feeding portion 12 is provided so that the hydrogen electrode 9 on the inner surface of the cylindrical electrochemical cell 1 serves as a cathode. Further, an oxygen electrode power supply unit 13 is installed so that the oxygen electrode 4 on the outer surface of the cylindrical electrochemical cell 1 is used as an anode.

  The unit container 2 can isolate the outside air from water vapor, oxygen and hydrogen in the unit container 2 and can maintain the pressure in the unit container 2.

  Further, the cell support plate 15 can isolate the generated oxygen and hydrogen. The steam introduction pipe 6 is fixed and supported on the steam introduction pipe support plate 16. Water vapor is introduced into the cylindrical electrochemical cell 1 through the water vapor introduction pipe 6.

  As described above, the ceramic cylindrical electrochemical cell 1 includes the hydrogen electrode 9, the oxygen electrode 11, and the electrolyte 10. Power is supplied to the hydrogen electrode 9 and the oxygen electrode 11 from a hydrogen electrode power supply unit 12 and an oxygen electrode power supply unit 13, respectively. By this power supply, water vapor is decomposed into oxygen ions and hydrogen at the hydrogen electrode 9. The decomposed oxygen ions pass through the electrolyte layer 10. The permeated oxygen ions are oxidized to oxygen at the oxygen electrode 11. Thus, the high-temperature steam electrolysis unit has a function of producing hydrogen and oxygen by being supplied with steam and electricity.

  When operating this high temperature steam electrolysis unit, the insulating seal means 7 is particularly important. The function of the insulating sealing means 7 is to electrically insulate between the ceramic cylindrical electrochemical cell 1 and the unit container 2, and to exist outside the cell and hydrogen existing inside the cylindrical electrochemical cell 1. It is to isolate the oxygen that does. The insulation seal 7 having sufficient soundness is a condition for stably producing hydrogen in the high-temperature steam electrolysis unit.

  The details of the electrically insulating insulating sealing means 7 interposed between the cylindrical electrochemical cell 1 and the unit container 2 will be described with reference to FIG.

  The cylindrical electrochemical cell 1 is configured to be fixed to a cell support plate 15 installed in a unit container 2 of a high-temperature steam electrolysis unit that is a hydrogen production apparatus. An insulating sealing means 7 is provided between the cell support plate 15 and the cylindrical electrochemical cell 1 to electrically insulate and seal the produced hydrogen under the ceramic cylindrical electrochemical cell 1. It has been. The insulating seal means 7 has an insulating component 21 that is an electrically insulating member. Between the insulating component 21 and the ceramic cylindrical electrochemical cell 1, a seal member 20 that forms a boundary that can withstand high temperatures is interposed between a hydrogen atmosphere and an oxygen atmosphere.

  As the insulating component 21, a ceramic that is stable even at a high temperature of 800 ° C. or more and excellent in electrical insulation is generally used. An example of this ceramic is alumina.

  The connection between the ceramic insulating component 21 such as alumina and the metal cell support plate 15 may be performed by a diffusion bonding method in which diffusion bonding is performed using an intermediate metal. By this diffusion bonding, ceramics and metal can be bonded and the insulating component 21 can be firmly fixed. The insulating component 21 is diffusion bonded to the connection component 23 made of the same material as the metal cell support plate 15, and then the insulation component 21, the connection layer 22, and the connection component 23 are bonded to the metal cell support plate 15. May be.

  A sealing member 20 is interposed between the insulating component 21 and the ceramic cylindrical electrochemical cell 1 to improve the sealing performance. As the seal member 20, a hollow metal O-ring or gasket capable of absorbing thermal expansion is used.

  In addition, there is a possibility that the ceramic cylindrical electrochemical cell 1 may move upward due to minute vibrations or an internal / external pressure difference of the cylindrical electrochemical cell 1. At this time, as shown in FIG. 3, a cell pressing plate 17 may be provided in the unit container 2 in order to suppress the upward movement of the cylindrical electrochemical cell 1. The cell retainer plate 17 is not intended to completely fix the ceramic cylindrical electrochemical cell 1 but can have an appropriate amount of movement (play) and does not hinder gas flow. A mesh is desirable.

  In the present embodiment configured as described above, a high-strength inorganic material such as alumina is used as an electrical insulating material at the lower end of the ceramic cylindrical electrochemical cell 1. Further, the insulating member 21 and the metal ring which is the cell support plate 15 in the unit container 2 are diffusion-bonded with an intermediate metal. A sealing member 20 that forms a boundary that can withstand high temperatures is provided between the insulating component 21 and the ceramic cylindrical electrochemical cell 1 to form a boundary that can withstand high temperatures between a hydrogen atmosphere and an oxygen atmosphere. ing.

  According to the present embodiment, a strong inorganic material such as alumina is used as an insulating material for a ceramic cylindrical electrochemical cell, and further, diffusion bonding is performed between the insulating member and the metal ring of the container by an intermediate metal. By doing so, a boundary that can withstand high temperatures can be formed between the hydrogen atmosphere and the oxygen atmosphere. Thus, an electrical insulation is maintained, an insulating seal that can maintain airtightness while maintaining mechanical strength is formed, and a high-temperature steam electrolysis reaction can be continuously performed.

  FIG. 4 is a longitudinal sectional view showing a configuration of a cylindrical electrochemical cell of the high temperature steam electrolysis unit according to the second embodiment of the present invention. In this figure, a water vapor introduction tube expansion / contraction absorbing member 18 is additionally provided at the lower portion of the water vapor introduction tube 6 of FIG. 1, and a cylindrical electrochemical cell expansion / contraction absorption member 19 is additionally provided at the lower portion of the cylindrical electrochemical cell 1. Therefore, the same or similar parts as those in FIG.

  As shown in the figure, a bellows or the like is provided between the lower portion of the water vapor introducing pipe 6 and the water vapor introducing pipe support plate 16 in the unit container 2 in order to absorb the expansion and contraction of the water vapor introducing pipe 6 in the axial direction. A water vapor introducing pipe expansion / contraction absorbing member 18 provided with the above is provided. By providing the water vapor introducing tube expansion / contraction absorbing member 18, the water vapor introducing tube 6 can absorb expansion and contraction and vibration caused by heat and mechanical action.

  A bellows is provided between the lower part of the cylindrical electrochemical cell 1 and the cylindrical electrochemical cell support plate 15 in the unit container 2 in order to absorb the expansion and contraction in the axial direction of the cylindrical electrochemical cell 1. A cylindrical electrochemical cell expansion / contraction absorbing member 19 provided with the above is provided on the cylindrical electrochemical cell support plate 15. Further, a socket-shaped connecting joint 14 is connected to the lower end of the ceramic cylindrical electrochemical cell 1 through an insulating seal 7 a which is an insulating seal means 7. The socket-shaped connection joint 14 will be described later.

  According to the present embodiment, the water vapor introducing pipe provided with a bellows or the like that absorbs expansion and contraction in the axial direction of the water vapor introducing pipe 6 between the water vapor introducing pipe 6 and the water vapor introducing pipe support plate 16 in the unit container 2. By providing the expansion / contraction absorbing member 18, it is possible to absorb expansion and contraction and vibration due to the action of heat and mechanical action of the water vapor introduction pipe 6. Thus, it is possible to absorb expansion and contraction and vibration due to the action of heat and mechanical action of the water vapor introduction pipe 6, and the possibility of damage to the cylindrical electrochemical cell 1 and this joint can be suppressed low.

  Further, a cylindrical electric cell provided with a bellows or the like for absorbing the expansion and contraction in the axial direction of the cylindrical electrochemical cell 1 between the cylindrical electrochemical cell 1 and the cylindrical electrochemical cell support plate 15 in the unit container 2. By providing the chemical cell expansion / contraction absorbing member 19, it is possible to absorb expansion / contraction and vibration due to heat and mechanical action of the cylindrical electrochemical cell 1. In this way, expansion and contraction and vibration due to heat and mechanical action of the cylindrical electrochemical cell 1 can be absorbed, and the possibility of damage to the cylindrical electrochemical cell 1 and this joint is suppressed to a low level. Can do. Thus, an insulating seal having electrical insulation and mechanical strength can be achieved, and high-temperature steam electrolysis can be continuously performed.

  FIG. 5 is a longitudinal sectional view showing the configuration of the cylindrical electrochemical cell of the high temperature steam electrolysis unit of the third embodiment of the present invention. In this figure, a socket-shaped connection joint 14 is additionally provided at the lower part of the cylindrical electrochemical cell 1 of FIG. 1 via an insulating seal 7a which is an insulating seal means 7, which is the same as or similar to FIG. These parts are denoted by the same reference numerals, and redundant description is omitted.

  As shown in this figure, the ceramic cylindrical electrochemical cell 1 is fixed to a cell support plate 15 in the unit container 2. Further, the water vapor introduction pipe 6 is fixed to the water vapor introduction pipe support plate 16 of the unit container 2 in a state where the water vapor introduction pipe 6 is disposed in the pipe of the ceramic cylindrical electrochemical cell 1.

  A socket-shaped connection joint 14 is connected to the lower part of the ceramic cylindrical electrochemical cell 1 through an insulating seal 7 a constituting the insulating seal means 7. The socket-shaped connection joint 14 is fixed to the cell support plate 15.

  In this embodiment configured as described above, by providing a socket-like connection joint 14 as a joint at the lower end of the ceramic cylindrical electrochemical cell 1, the strength of the joint is increased compared to the butt joint. is doing.

  Further, as a material of the socket-shaped connection joint 14, a material having a thermal expansion coefficient similar to that of the ceramic cylindrical electrochemical cell 1 is used, and between the ceramic cylindrical electrochemical cell 1 and the socket-shaped connection joint 14. As the material of the insulating seal 7a, a material having a thermal expansion coefficient very close to that of the ceramic cylindrical electrochemical cell 1 is used. By using such a material having a similar coefficient of thermal expansion, it is possible to suppress breakage due to thermal expansion and contraction due to a temperature change during operation.

  According to the present embodiment, the connection portion between the lower end of the cylindrical electrochemical cell 1 and the insulating seal 7a is provided on the cell support plate 15 as a joint portion of the ceramic cylindrical electrochemical cell 1 at the lower end. By providing the socket-shaped connection joint 14, the strength of the joint can be increased as compared with the butt joint. Furthermore, by using a material having a similar thermal expansion coefficient as the socket-shaped connection joint 14, it is possible to suppress breakage due to thermal expansion and contraction due to a temperature change during operation. Thus, the electrical insulation is maintained, and the airtightness can be maintained while maintaining the mechanical strength, so that the high temperature steam electrolysis reaction can be continued.

  FIG. 6 is a longitudinal sectional view showing a configuration of a cylindrical electrochemical cell of a high-temperature steam electrolysis unit according to the fourth embodiment of the present invention. This figure is obtained by adding a steam introduction pipe expansion / contraction absorbing member 18 to the lower part of the steam introduction pipe 6 of FIG. 5, and the same or similar parts as in FIG. Description is omitted.

  As shown in the figure, a bellows or the like is provided between the lower portion of the water vapor introducing pipe 6 and the water vapor introducing pipe support plate 16 in the unit container 2 in order to absorb the expansion and contraction of the water vapor introducing pipe 6 in the axial direction. A water vapor introducing pipe expansion / contraction absorbing member 18 provided with the above is provided.

  In the present embodiment configured as described above, when the cylindrical electrochemical cell 1 is fixed in the unit container 2, the insulating seal 7a which is a connecting portion between the metal part (container) and the ceramics (cell). As glass is used. Since this glass is used, the strength of this portion is weak and easily damaged by vibration or the like, and straight joining is difficult. Here, the water vapor introducing pipe expansion / contraction absorbing member 18 provided with a bellows or the like is provided in the water vapor introducing pipe 6.

  According to the present embodiment, by providing this water vapor introducing tube expansion / contraction absorbing member 18, the water vapor introducing tube 6 can absorb expansion and contraction due to heat and mechanical action. Thus, the possibility of damage to the cylindrical electrochemical cell 1 and the joint can be suppressed to a low level.

  FIG. 7 is a longitudinal sectional view showing the configuration of the cylindrical electrochemical cell 1 of the high-temperature steam electrolysis unit according to the fifth embodiment of the present invention. In this figure, a cylindrical electrochemical cell expansion / contraction absorbing member 19 is additionally provided at the bottom of the cylindrical electrochemical cell 1 in FIG. 6, and the same or similar parts as in FIG. Therefore, the duplicate description is omitted.

  As shown in the figure, between the lower part of the cylindrical electrochemical cell 1 and the cylindrical electrochemical cell support plate 15 in the unit container 2, the expansion and contraction in the axial direction of the water vapor introducing pipe 6 is absorbed. Further, a cylindrical electrochemical cell expansion / contraction absorbing member 19 provided with a bellows or the like is provided.

  In the present embodiment configured as described above, the cylindrical electrochemical cell 1 is fixed in the unit container 2. At this time, glass is used for the insulating seal 7a which is a connection portion between the metal part (container) and the ceramic (cell). Since this glass is used, the strength of this portion is weak and easily damaged by vibration or the like, and straight joining is difficult. Here, a cylindrical electrochemical cell expansion / contraction absorbing member 19 provided with a bellows or the like is provided.

  According to the present embodiment, by providing the cylindrical electrochemical cell expansion / contraction absorbing member 19, the cylindrical electrochemical cell 1 can absorb expansion and contraction due to heat and mechanical action. Thus, the possibility of damage to the cylindrical electrochemical cell 1 and the joint can be suppressed to a low level.

  Furthermore, the present invention is not limited to the above-described embodiments, and various modifications can be made without departing from the spirit of the present invention by combining the embodiments of the present invention. it can.

The schematic longitudinal cross-sectional view which shows the structure of the high temperature steam electrolysis unit of the 1st Embodiment of this invention. The longitudinal cross-sectional view which shows the fixing method of the cylindrical electrochemical cell of FIG. The longitudinal cross-sectional view which shows the other fixing method of the cylindrical electrochemical cell of FIG. The longitudinal cross-sectional view which shows the structure of the cylindrical electrochemical cell of the high temperature steam electrolysis unit of the 2nd Embodiment of this invention. The longitudinal cross-sectional view which shows the structure of the cylindrical electrochemical cell of the high temperature steam electrolysis unit of the 3rd Embodiment of this invention. The longitudinal cross-sectional view which shows the structure of the cylindrical electrochemical cell of the high temperature steam electrolysis unit of the 4th Embodiment of this invention. The longitudinal cross-sectional view which shows the structure of the cylindrical electrochemical cell of the high temperature steam electrolysis unit of the 5th Embodiment of this invention.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Cylindrical electrochemical cell, 2 ... Unit container, 3 ... Steam supply part, 4 ... Product hydrogen outlet part, 5 ... Product oxygen outlet part, 6 ... Steam inlet pipe, 7 ... Insulation seal means, 7a ... Insulation seal, DESCRIPTION OF SYMBOLS 8 ... Base tube, 9 ... Hydrogen electrode, 10 ... Electrolyte layer, 11 ... Oxygen electrode, 12 ... Hydrogen electrode feeding part, 13 ... Oxygen electrode feeding part, 14 ... Connection joint, 15 ... Cell support plate, 16 ... Water vapor introducing pipe Support plate, 17 ... cell pressing plate, 18 ... bellows (water vapor introducing tube expansion / contraction absorption member), 19 ... bellows (cylindrical electrochemical cell expansion / contraction absorption member), 20 ... gasket (sealing member), 21 ... insulating member, 22 ... connection layer, 23 ... connection parts.

Claims (12)

A hydrogen electrode that closes one end and forms a cylindrical inner side, a cylindrical oxygen electrode provided outside the hydrogen electrode, and an electronic insulating property and oxygen ion conductivity provided between the hydrogen electrode and the oxygen electrode A cylindrical electrochemical cell made of ceramics, including an electrolyte layer having
A water vapor introduction pipe installed inside the cylindrical electrochemical cell to introduce water vapor;
A unit container for storing the cylindrical electrochemical cell;
A cell support plate fixed in the unit container and supporting the cylindrical electrochemical cell;
Insulating sealing means provided between the cell support plate and the cylindrical electrochemical cell for electrically insulating and sealing the produced hydrogen;
A water vapor inlet tube support plate fixed in the unit container and supporting the water vapor inlet tube;
A hydrogen electrode power feeding portion provided so as to make the hydrogen electrode on the inner surface of the cylindrical electrochemical cell a cathode;
An oxygen electrode feeding portion provided so as to make the oxygen electrode on the outer surface of the cylindrical electrochemical cell an anode;
The hydrogen production apparatus characterized by having.   The hydrogen production apparatus according to claim 1, wherein the unit container further includes a cell pressing plate that presses an upper portion of the cylindrical electrochemical cell.   The insulating sealing means includes an electrically insulating member provided between the cell support plate and the cylindrical electrochemical cell, and a sealing member that seals between the electrically insulating member and the cylindrical electrochemical cell. The hydrogen production apparatus according to claim 1, comprising:   The hydrogen production apparatus according to claim 2, wherein the electrically insulating member and the cell support plate are connected by diffusion bonding.   2. The hydrogen according to claim 1, wherein the water vapor introduction pipe includes a water vapor introduction pipe expansion and contraction absorbing member that absorbs expansion and contraction in the axial direction of the water vapor introduction pipe between the water vapor introduction pipe support plate. Manufacturing equipment.   The hydrogen production apparatus according to claim 5, wherein the water vapor introduction pipe expansion and contraction absorbing member includes a bellows.   The cylindrical electrochemical cell includes a cylindrical electrochemical cell expansion and contraction absorbing member that absorbs expansion and contraction in the axial direction of the cylindrical electrochemical cell between the cylindrical electrochemical cell support plate and the cylindrical electrochemical cell support plate. The hydrogen production apparatus according to claim 1.   The hydrogen production apparatus according to claim 7, wherein the cylindrical electrochemical cell expansion and contraction absorbing member includes a bellows.   The insulating sealing means is provided on the cell support plate so as to surround an insulating seal provided at a lower end of the cylindrical electrochemical cell for insulating and sealing, and a connecting portion between the lower end of the cylindrical electrochemical cell and the insulating seal. The hydrogen production apparatus according to claim 1, further comprising: a socket-shaped connection joint.   10. The hydrogen production apparatus according to claim 9, wherein the insulating seal is made of ceramics having a thermal expansion coefficient close to that of the cylindrical electrochemical cell.   10. The hydrogen production apparatus according to claim 9, wherein the socket-shaped connection joint is made of ceramics having a thermal expansion coefficient close to that of the cylindrical electrochemical cell. A hydrogen electrode that closes one end and forms a cylindrical inner side, a cylindrical oxygen electrode provided outside the hydrogen electrode, and an electronic insulating property and oxygen ion conductivity provided between the hydrogen electrode and the oxygen electrode A cylindrical electrochemical cell manufacturing step for manufacturing a cylindrical electrochemical cell from ceramics,
A water vapor introduction step for introducing water vapor into the inside of the cylindrical electrochemical cell, which is fixed in the unit container, via a water vapor introduction pipe;
A hydrogen electrode feeding step in which the cathode on the inner surface of the cylindrical electrochemical cell is used as a cathode;
An oxygen electrode feeding step in which the oxygen electrode on the outer surface of the cylindrical electrochemical cell is used as an anode;
A hydrogen generation step for generating hydrogen via the cylindrical electrochemical cell;
An insulating sealing step for electrically insulating the cell support plate fixed in the unit container and the cylindrical electrochemical cell and sealing the produced hydrogen;
A method for producing hydrogen, comprising:

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